Cyclopropane esters for the control of mites

ABSTRACT

Esters of cyclopropyl substituted carboxylic acids, syntheses thereof, compositions thereof, and use for the control of mites and ticks.

This is a division of application Ser. No. 504,224, filed Sept. 9, 1974,U.S. Pat. No. 3,957,849.

This invention relates to novel compounds, synthesis thereof,compositions thereof, and the control of mites.

The compounds of the present invention are effective for the control ofmites and especially spider mites. Spider mites are plant feeders andcause serious damage to orchard trees, field crops, greenhouse plantsand other vegetation. They feed on the foliage and fruit of plants andtrees and attack a variety of plants and trees due to their widedistribution and polyphagous feeding habits. Spider mites of the familyTetranychidae, such as Tetranychus urticae, Tetranychus canadensis,Tetranychus cinnabarinus, Tetranychus pacificus, Bryobia praetiosa,Oligonychus pratensis, Oligonychus ilicis, Panonychus citri, Panonychusulmi, and similar related species, are of particular biological interestand economic importance. Other mites are those of the familyTarsonemidae, such as Steneotarsonemus pallidus.

Compounds of the present invention of the following formula I areeffective control agents for mites. ##STR1## wherein,

R is alkyl of one to eighteen carbon atoms, alkenyl of two to eighteencarbon atoms, alkynyl of two to eighteen carbon atoms, cycloalkyl, aryl,or aralkyl, each of said cycloalkyl, aryl, or aralkyl rings beingoptionally substituted by one or two alkyl, alkoxy, halogen or nitrogroups;

R' is ---CH=CH--or --(CH₂)_(p) -- in which p is an even integer from twoto 20;

R" is ethylene or propylene;

X is oxygen or sulfur;

n is zero or one; and

n' is one, two or three;

With the proviso that each compound contains at least twelve carbonatoms in the molecule.

Hereinafter, each of R, R', R", X, n, n' and p is as defined aboveunless otherwise specified.

The compounds of formula I are applied to the mite during the egg,larval or nymphal stages in view of their effect in causing inhibitionof egg hatching, abnormal development leading to death, inability topass from one stage to the next, or inability to reproduce. Some of thecompounds also exhibit a residual ovicidal effect on foliage. A compoundof formula I can be applied at concentration levels of the order of0.001% to 1%, usually 0.01 to 0.1% by weight. Suitable carriersubstances include liquid or solid inert carriers, such as water,acetone, xylene, mineral or vegetable oils, talc, vermiculite, andsilica. Treatment of mites in accordance with the present invention canbe accomplished by spraying, dusting, or otherwise contacting the mitesand/or their eggs or larvae directly or indirectly. Generally, aconcentration of less than 25% of active compound in the formulation isused depending on the type of application apparatus. The formulationscan include emulsifying agents and wetting agents to assist in theapplication and effectiveness of the active ingredient.

The esters of formula I can be prepared by reacting the appropriatemono-hydric alcohol R--X-R"]_(n) _(') OH with one mole of an acid of theformula ##STR2## in the presence of an acid catalyst and with heating.The reaction can be carried out in the absence of a solvent; however,use of a solvent inert to the reaction, such as an ether or hydrocarbonsolvent, is preferred. Water may be removed by azeotropic distillation,if desired.

Alternatively, the appropriate acid halide ##STR3## may be reacted withthe corresponding mono-hydric alcohol in the presence of pyridine and ateither room temperature or, when the alcohol is sensitive to mineralacid, at from about -10° to about 0° C.

Many of the monohydric alcohols used in the preparation of novelcompounds of this invention are commercially available. Typical of theseare the monomethyl ether of ethylene glycol and the monomethyl ether ofpropylene glycol.

Alcohols of the formula R--O--R"]_(n) _(') OH where n' is one can beprepared by reacting ethylene oxide or propylene oxide with an alcoholROH in the presence of a sodium alkoxide at a temperature of from 35° to70° C or by reacting ethylene chlorohydrin or propylene chlorohydrinwith an alcohol ROH in the presence of sodium. For those alcohols wheren' is two, the above process is repeated with the alcohol R-- OR"] OHfrom that process being reacted with the ethylene oxide or propyleneoxide in the presence of a sodium alkoxide. The process is againrepeated to yield those alcohols where n' is three.

Alcohols of the formula R-- S--R"]_(n) _(') OH can be prepared byreacting ethylene chlorohydrin or 2-chloropropanol with a thiol RSH inthe presence of sodium at from 30° to 150° C. To prepare those alcoholswhere n' is two or three, the compound R--S--R"]_(n) _(') OH is treatedwith toluenesulfonyl chloride followed by NaSH and dimethyl formamide.The resultant thiols RS--(R")n' --SH are then reacted with ethylenechlorohydrin or 2-chloropropanol as above to yield those alcohols wheren' is two. The entire sequence is again repeated to obtain thosecompounds where n' is three.

The syntheses of the acids ##STR4## and acid chlorides are described incopending Ser. No. 461,189, filed Apr. 12, 1974, now U.S. Pat. No.3,925,460, and copending Ser. No. 489,207, filed July 17, 1974 now U.S.Pat. No. 3,960,907, the disclosures of which are hereby incorporated byreference.

The term "alkyl," as used herein, refers to a straight or branched chainsaturated aliphatic hydrocarbon group of 1 to 18 carbon atoms, e.g.methyl, ethyl, propyl, octyl, 2-methyloctyl, undecyl, pentadecyl, andthe like. The term "lower alkyl" refers to an alkyl group of 1 to 6carbon atoms.

The term "alkenyl," as used herein, refers to a straight or branchedchain hydrocarbon group of 2 to 18 carbon atoms having one or two sitesof olefinic unsaturation.

The term "alkynyl," as used herein, refers to a straight or branchedchain hydrocarbon group of 2 to 18 carbon atoms having one or two sitesof acetylenic unsaturation.

The term "cycloalkyl," as used herein, refers to a mono-valentcycloalkyl moiety of 4 to 8 carbon atoms, i.e. cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, and cyclooctyl.

The term "aryl," as used herein, refers to a monovalent aromatichydrocarbon group containing from 6 to 14 carbon atoms, such as phenyl,biphenyl, and naphthyl.

The term "aralkyl," as used herein, refers to a monovalent hydrocarbongroup containing from 7 to 15 carbon atoms in which a hydrogen atom ofan alkyl group having a chain length of 1 to 6 carbon atoms issubstituted by an aryl group, such as benzyl, phenethyl, methylbenzyl,naphthylmethyl and naphthylethyl.

The term "alkoxy," as used herein, refers to a straight or branchedchain saturated aliphatic hydrocarbonoxy group of 1 to 15 carbon atoms,e.g., methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, n-heptyloxy,n-dodecyloxy, 2-methyloctyloxy, and the like.

The term "halogen," as used herein, refers to fluorine, chlorine, andbromine.

The esters of the present invention can be used alone or in inertcarrier substance for the control of mites (Acarina) or can be used inmixture with pesticides and/or juvenile hormone analogs known in the artin order to obtain a broader spectrum of activity. Suitable insecticidesinclude Baygon, Captan, Sevin, Ciodrin, Systox, Diazinon, Vapona,Galecron, Cygon, Dimethrin, Dursban, Malathion, and Parathion. Typicaljuvenile hormone analogs which can be used in mixture with the compoundof the present invention are described in U.S. Pat. Nos. 3,752,843 and3,755,411.

The esters of the present invention are useful for the control of mitesand ticks which are ectoparasitic on domestic animals including birds.The compounds can be applied in either solution or in powder (dust) formin a conventional manner.

The following examples are provided to illustrate the synthesis of theesters of the present invention and the practice of the presentinvention. Temperature is in degrees Centigrade. All boiling points weremeasured by short path distillation.

EXAMPLE 1

To 14.0 ml. of anhydrous 1-pentanol in 100 ml. tetrahydrofuran is added0.25 g. sodium. After the sodium has reacted, gaseous ethylene oxide(0.34 g.) is added at a rate such that the temperature is maintainedbetween 35° and 40°. The flask is sealed and allowed to stand for oneday. The reaction mixture is poured into water and then extracted withether, dried over sodium sulfate, the solvent and the residue distilledand fractionated to yield 2-pentyloxy-1-ethanol.

Using the procedure of Example 1, each of ethylene oxide and propyleneoxide is reacted with each of 1-dodecanol, 1-tridecanol, 1-tetradecanol,1-pentadecanol, cyclohexanol, phenol, benzyl alcohol, 4-methoxyphenol,4-methylphenol, 2-decyn-1-ol, tetradeca-10,12-dien-1-ol,hexadec-9en-1-ol, octadec-9-yn-1-ol and 7-methyltrideca-5,8-diyn-7-ol toyield the alcohols of column I.

I

2-(dodecyloxy)ethanol

2-(dodecyloxy)-1-methylethan-1-ol

2-(tridecyloxy)ethanol

1-methyl-2-tridecyloxyethan-1-ol

2-(tetradecyloxy)ethanol

1-methyl-2-(tetradecyloxy)ethan-1-ol

2-(pentadecyloxy)ethanol

1-methyl-2-(pentadecyloxy)ethan-1-ol

2-(cyclohexyloxy)ethanol

2-(cyclohexyloxy)-1-methylethan-1-ol

2-(phenoxy)ethanol

1-methyl-2-(phenoxy)ethan-1-ol

2-(benzyloxy)ethanol

2-(benzyloxy)-1-methylethan-1-ol

2-(4-methoxyphenoxy)-1-ethanol

2-(4-methoxyphenoxy)-1-methyl-1-ethanol

2-(4-methylphenyl)ethan-1-ol

2-(4-methylphenoxy)-1-methylethan-1-ol

2-decynyloxyethanol

2-decynyloxy-1-methylethan-1-ol

tetradeca-10,12-dienloxyethanol

1-methyl-2-tetradeca-10,12-dienyloxyethan-1-ol

2-hexadec-9-enyloxyethan-1-ol

2-hexadec-9-enyloxy-1-methylethan-1-ol

2-octadec-9-ynyloxyethan-1-ol

1-methyl-2-octadec-9-ynyloxyethan-1-ol

2-(7-methyltrideca-5,8-diyn-7-yloxy)ethan-1-ol

1-methyl-2-(7-methyltrideca-5,8-diyn-yloxy)ethan-1-ol

EXAMPLE 2

To a mixture of 0.25 g. sodium hydride in 25 ml. anhydroustetrahydrofuran is added 0.5 g. methanethiol. The reaction mixture isstirred for 2 hours and the solvent is then removed by evaporation. Tothe residue is added, at 35° , 5 ml. water and 6 g. of 20% aqueousethylene chlorohydrin. The reaction mixture is stirred for 30 minutesand then refluxed for 1 hour. After cooling to room temperature, etheris added, the organic phase is separated and washed in turn with 10%aqueous sodium bicarbonate, water, 2N sulfuric acid, water, and brine.The solution is dried over calcium carbonate and the solvent is removedby evaporation to yield 2-methylthio-1-ethanol.

Following the procedure of Example 2, each of ethylene chlorohydrin and1-chloro-2-propanol is reacted with each of 1-dodecanethiol,1-tetradecanethiol, 1-butanethiol, benzenethiol, cyclohexanethiol,1-propanethiol and 2-methylthio-1-ethanethiol to yield the alcohols ofcolumn II.

II

2-(dodecylthio)ethanol

1-methyl-2-(dodecylthio)ethanol

2-(tetradecylthio)ethanol

1-methyl-2-(tetradecylthio)ethan-1-ol

2-(butylthio)ethanol

2-(butylthio)-1-methylethan-1-ol

2-(phenylthio)ethanol

1-methyl-2-(phenylthio)ethan-1-ol

2-(cyclohexylthio)ethanol

2-(cyclohexylthio)-1-methylethan-1-ol

2-(propylthio)ethanol

1-methyl-2-(propylthio)ethan-1-ol

3,6-dithiaheptanol

3,6-dithia-1-methylheptanol-2-ol

EXAMPLE 3

A. To a mixture of 9.6 g. 1-tridecanol and 100 ml. tetrahydrofuran at 0°is added 33.5 ml. of 1.43 M n-butyllithium in hexane over a 5 minuteperiod. The reaction mixture is allowed to warm to room temperature andis stirred for 1 hour. The solvent is removed by evaporation and to thecolorless viscous residue is added 100 ml. tetrahydrofuran and 50 ml.hexamethylphosphoric triamide followed by 20 g. sodium iodoacetate. Themixture is stirred at room temperature overnight and then boiled for 8.5hours. After cooling to room temperature, 150 ml. methanol, 75 ml.water, and 3.8 g. sodium hydroxide pellets are added. The mixture isboiled for 12 hours, cooled to room temperature, and allowed to stand 15days. The solvent is removed by evaporation and to the residue is added400 ml. of a 2:1 mixture of ether and pentane and 200 ml. water. The toptwo phases of the resultant triphasic mixture are separated and washedtwice with 100 ml. portions of water. Ethyl acetate, water and sulfuricacid are added; after vigorous shaking the mixture is filtered and thefiltrate is washed two times with 50 ml. portions of sodium chloride andthen dried over calcium sulfate.

B. To a mixture of 2.58 g. 3-oxahexadecanoic acid and 15 ml. anhydroustetrahydrofuran at 0° is added 12 ml. of a 1M diborane intetrahydrofuran solution. The ice-bath is removed after the bubblingstops and the mixture is stirred overnight. Slowly, 20 ml. water isadded and the solution is stirred 15 minutes after the initial bubblingceases. Ester (100 ml.), water (100 ml.) and aqueous 3N sulfuric acid(30 ml.) are added and the organic phase is separated and washed in turnwith 40 ml. water and 40 ml. aqueous saturated sodium chloride and thendried over calcium sulfate. Solvent is removed by evaporation to yield1.75 g. 3-oxahexadecanol, to which is added 60 ml. anhydrous ether. Thesolution is cooled to 0° and 1.12 g. cyclopropane carboxylic acidchloride and 1.2 ml. pyridine is added. The reaction mixture is allowedto warm to room temperature and is stirred for 4 days. The mixture isthen filtered, 1 ml. water is added and the solution is stirred for 18hours. Ether (50 ml.), pentane (50 ml.), and water (100 ml.) are addedand the mixture is acidified with aqueous 3N sulfuric acid. The organiclayer is separated and washed, in turn, with aqueous 15% potassiumcarbonate (1 × 50 ml.), water (2 × 50 ml.), aqueous saturated coppersulfate (1 × 50 ml.), water (1 × 50 ml.), aqueous saturated sodiumchloride (1 × 50 ml.) and dried over calcium sulfate. The solvent isremoved by evaporation to yield 1.70 g. 3-oxahexadecylcyclopropanecarboxylate.

Following the procedure of Example 3, 3-oxahexadecanol is reacted witheach of 3-cyclopropylpropionyl chloride and 3-cyclopropyl-2-propenoylchloride to yield the esters of column III.

III

3-oxahexadecyl 3-cyclopropylpropionate

3-oxahexadecyl 3-cyclopropyl-2-propenoate

EXAMPLE 4

To a mixture of 2.0 g. cyclopropanecarboxylic acid chloride, 60 ml.anhydrous ether, and 2.56 g. 3,6,9-trioxaundecanol, at 0° , is added 2.3ml. pyridine. The reaction mixture is stirred at room temperature andthen is filtered, 1 ml. water is added to the filtrate and the mixtureis stirred overnight. Ether (50 mi.), pentane (50 ml.), and water (100ml.) are added and the mixture is acidified with 3N sulfuric acid. Themixture is worked up using the procedure of Example 3 to yield 1.30 g.of 3,6,9-trioxaundecyl cyclopropanecarboxylate, b.p. 86° -94° (0.03 mm).

Following the procedure of Example 4, each of cyclopropanecarboxylicacid chloride and 3-cyclopropylpropionyl chloride is reacted with eachof the alcohols of column IV to yield the esters of this invention,representative members of which are listed in column V.

IV

3,6,9-trioxatridecanol

2-(dodecyloxy)ethanol

2-(dodecyloxy)methyl-1-ethanol

2-(tridecyloxy)ethanol

1-methyl-2-tridecyloxyethanol

2-(tetradecyloxy)ethanol

1-methyl-2-(tetradecyloxy)ethanol

2-(pentadecyloxy)ethanol

1-methyl-2-(pentadecyloxy)ethanol

2-(cyclohexyloxy)ethanol

2-(cyclohexyloxy)-1-methylethanol

2-(phenoxy)ethanol

1-methyl-2-(phenoxy)ethanol

2-(benzyloxy)ethanol

2-(benzyloxy)-1-methylethanol

2-(4-methoxyphenyl)ethanol

1-methyl-2-(4-methoxyphenyl)ethanol

2-(4-methylphenyl)ethanol

1-methyl-2-(4-methylphenyl)ethanol

V

3,6,9-trioxatridecyl cyclopropanecarboxylate

2-(dodecyloxy)ethyl cyclopropanecarboxylate

2-dodecyloxy-1-methylethyl cyclopropanecarboxylate

1-methyl-2-(tridecyloxy)ethyl cyclopropanecarboxylate

2-(tetradecyloxy)ethyl-3-cyclopropylpropionate

1-methyl-2-(tetradecyloxy)ethyl 3-cyclopropylpropionate

2-(pentadecyloxy)ethyl cyclopropanecarboxylate

1-methyl-2-(pentadecyloxy)ethyl 3-cyclopropylpropionate

2-(cyclohexyloxy)ethyl cyclopropanecarboxylate

2-(cyclohexyloxy)-1-methylethyl 3-cyclopropylpropionate

2-(phenoxy)ethyl 3-cyclopropylpropionate

1-methyl-2-(phenoxy)ethyl cyclopropanecarboxylate

2-(benzyloxy)ethyl cyclopropanecarboxylate

2-benzyloxy-1-methylethyl 3-cyclopropylpropionate

2-(4-methoxyphenyl)ethyl 3-cyclopropylpropionate

2-(4-methoxyphenyl)-1-methylethyl 3-cyclopropylpropionate

2-(4-methylphenyl)ethyl cyclopropanecarboxylate

2-(4-methylphenyl)-1-methylethyl cyclopropanecarboxylate

EXAMPLE 5

To a mixture of 2.0 g. 2-hydroxyethyl dodecyl sulfide, 60 ml. anhydrousether and 1.27 g. cyclopropyl carboxylic acid chloride at 0° is added1.3 ml. pyridine. The mixture is allowed to warm to room temperature andis stirred for three days. The product is isolated using the procedureof Example 3 to yield 3-thiapentadecyl cyclopropanecarboxylate, boilingpoint 131° -137°137° (0.03 mm.).

Following the procedure of Example 5, the compounds of column II arereacted with each of cyclopropanecarboxylic acid chloride,3-cyclopropylpropionyl chloride, 5-cyclopropylpentanoyl chloride,7-cyclopropylheptanoyl chloride and 9-cyclopropylnonanoyl chloride toyield the esters of this invention, representative examples of which arelisted in column VI.

VI

2-(tetradecylthio)ethyl cyclopropanecarboxylate

1-methyl-2-(tetradecylthio)ethyl 3-cyclopropylpropionate

2-(butylthio)ethyl 5-cyclopropylpentanoate

2-(butylthio)-1-methylethyl 7-cyclopropylheptanoate

2-(phenylthio)ethyl 3-cyclopropylpropionate

1-methyl-2-(phenylthio)ethyl cyclopropanecarboxylate

2-(cyclohexylthio)ethyl 3-cyclopropylpropionate

2-(cyclohexylthio)-1-methylethyl 5-cyclopropylpentanoate

2-(propylthio)ethyl 7-cyclopropylheptanoate

1-methyl-2-(propylthio)ethyl 9-cyclopropylnonanoate

3,6-dithiaheptyl 7-cyclopropylheptanoate

4,7-dithiaoctyl 5-cyclopropylpentanoate

EXAMPLE 6

To a mixture of 3.5 g. 2-(4-biphenyloxy)ethanol, 80 ml. anhydroustetrahydrofuran, and 2.56 g. cyclopropanecarboxylic acid chloride, at 0°, is added 2.6 ml. pyridine. The reaction mixture is allowed to warm toroom temperature and then is stirred for 9 days. The mixture is filteredand to the filtrate is added 0.5 ml. water followed by stirring for 6hours at room temperature. Solvent is removed by evaporation and to theresidue is added 100 ml. ether, 60 ml. ethyl acetate, and 150 ml. water.The organic layer is separated, acidified with 3N sulfuric acid andwashed in turn with aqueous 10% potassium carbonate, water, saturatedaqueous copper sulfate, water, and saturated aqueous sodium chloride,dried over calcium sulfate and the solvent removed to yield 2.13 g.biphenyloxyethyl cyclopropanecarboxylate as pale yellow crystals.

Following the procedure of Example 6, 2-naphthyloxyethylcyclopropanecarboxylate and 2-(2-phenoxyethoxy)ethylcyclopropanecarboxylate are prepared from cyclopropanecarboxylic acidchloride and each of 2-(naphthyloxy)ethanol and2-(2-phenoxyethoxy)ethanol.

EXAMPLE 7

To a mixture of 1.88 g. 2-(4-chlorophenylthio)ethanol and 1.35 g.cyclopropylcarboxylic acid chloride in 50 ml. ether is added 2equivalents pyridine. The reaction mixture is stirred overnight at roomtemperature and worked up as in Example 5 to yield2-(4-chlorophenylthio)ethyl cyclopropanecarboxylate.

A wettable powder suitable for field application after dilution can beformulated by blending and then air-mailing a mixture of 20 to 30% of anester of this invention, 60 to 70% of a solid carrier such as AttaclayX-250, 1 to 3% of an anionic surfactant, such as Igepon T-77, and 3 to5% of a dispersing agent such as Marasperse N-22.

A typical formulation is as follows:

    ______________________________________                                        Active ingredient.sup.1                                                                              25.0%                                                  Synthetic calcium silicate                                                                           40.0%                                                  Attapulgite Clay       29.0%                                                  Sodium lignosulfonate  4.0%                                                   Sodium N-methyl N-oleoyl taurate                                                                     2.0%                                                   ______________________________________                                        .sup.1 The active ingredient is selected from one or more of the              following:                                                                    3-thiapentadecyl cyclopropanecarboxylate                                      3-thiapentadecyl 3-cyclopropylpropionate                                      3-oxahexadecyl cyclopropanecarboxylate                                        2-(4-chlorophenylthio)ethyl cyclopropanecarboxylate                       

The mite control agents of the present invention can be used alone in aninert agriculturally acceptable carrier substance for the control ofmites (Acarina) or can be used in mixture with insecticides and/orjuvenile hormone analogs known in the art to provide a broader spectrumof activity on more developmental stages of the mites or on otherpestiferous insect species.

The effectiveness of the compunds of the present invention isdemonstrated below.

Adults of Tetranychus urticae are allowed to oviposit for 24 hours oncastor bean leaf discs (diameter 1 cm.) on moist cottonwool.

After 24 hours, the adults are removed and the leaf discs are thendipped in acetone solutions of the compound being tested.

After submersion for one second, the solvent on the leaf discs isallowed to dry and the leaf discs are then glued to a plastic petri dishto prevent crumpling.

Six days later (when all the viable eggs on untreated discs haveemerged), the number of unhatched eggs is calculated as a percentage ofthe total number originally present and corrected for any spontaneousnon-emergence observed in control discs treated only with solvent(Abbott correction).

Table 1 presents the results of biological testing conducted as outlinedabove.

                  TABLE I                                                         ______________________________________                                                          % Concentration                                                                           Reduction of                                    Compound          in solution Hatching in %                                   ______________________________________                                        3-oxahexadecyl cyclopropanecar-                                                                 0.1         95                                              boxylate                                                                      2-(4-chlorophenylthio)ethyl                                                                     0.1         97                                              cyclopropanecarboxylate                                                       3-thiapentadecyl cyclopropane-                                                                  0.1         100                                             carboxylate                                                                   ______________________________________                                    

We claim:
 1. A method for the control of mites of the familyTetranychidae and the family Tarsonemidae which comprises contacting themite at the egg or larval stage with an ovicidally effective amount orlarvacidally effective amount of a compound of formula (I): ##STR5##wherein, R is alkyl of one to eighteen carbon atoms, alkenyl of two toeighteen carbon atoms, alkynyl of two to eighteen carbon atoms,cyclohexyl, phenyl, biphenyl or benzyl, each of said cyclohexyl, phenyl,biphenyl or benzyl being optionally substituted by one or two groupsselected from the group consisting of methyl, ethyl, methoxy, ethoxy,chloro and nitro;R' is --CH=CH-- or --(CH₂)_(p) - in which p is an eveninteger from two to twenty; R" is ethylene or propylene; X is oxygen orsulfur; n is zero or one; and n' is 1, 2 or 3, with the proviso thateach compound contains at least 12 carbon atoms.
 2. The method accordingto claim 1 wherein the compound is 3-oxahexadecylcyclopropanecarboxylate.
 3. The method according to claim 1 wherein thecompound is 2-(4-chlorophenylthio)ethyl cyclopropanecarboxylate.
 4. Themethod according to claim 1 wherein the compound is a compound of theformula: ##STR6## wherein X is oxygen or sulfur and R is dodecyl ortridecyl.
 5. The method according to claim 4 wherein the compound is3-thiapentadecyl cyclopropanecarboxylate.
 6. The method according toclaim 4 wherein the compound is 3-oxapentadecyl cyclopropanecarboxylate.7. A composition for the control of mites of the family Tetranychidae orthe family Tarsonemidae which comprises a suitable carrier substance anda compund of formula (I): ##STR7## wherein, R is alkyl of 1 to 18 carbonatoms, alkenyl of 2 to 18 carbon atoms, alkynyl of 2 to 18 carbon atoms,cyclohexyl, phenyl, biphenyl or benzyl, each of said cyclohexyl, phenyl,biphenyl or benzyl being optionally substituted by one or two groupsselected from the group consisting of methyl, ethyl, methoxy, ethoxy,chloro and nitro;R' is --CH=CH-- or (CH₂)_(p) -- in which p is an eveninteger from 2 to 20; R" is ethylene or propylene; X is oxygen orsulfur; n is 0 or 1; and n' is 1, 2 or 3, with the proviso that eachcompound contains at least 12 carbon atoms, said compound being presentin the composition in an ovicidally effective amount or larvicidallyeffective amount.
 8. The composition according to claim 7 wherein thecompound is a compound of the formula ##STR8## wherein X is oxygen orsulfur and R is dodecyl or tridecyl.
 9. The composition according toclaim 7 wherein the compound is 3-oxahexadecyl cyclopropanecarboxylate.10. The composition according to claim 7 wherein the compound is3-thiapentadecyl cyclopropanecarboxylate.
 11. The composition accordingto claim 7 wherein the compound is 3-oxapentadecylcyclopropanecarboxylate.
 12. The composition according to claim 7wherein the compound is 2-(4-chlorophenylthio)ethylcyclopropanecarboxylate.